JPH02228675A - Compound containing organic sulfur as auxiliary agent for positive type electrostatic liquid developer - Google Patents

Abstract

PURPOSE: To improve the electrostatic charge and imaging characteristics by using a nonpolar liq. having a kauri-butanol value of <=30 and thermoplastic resin particles having a certain particle size and contg. a specified org. sulfer- contg. compd. dispersed as an auxiliary. CONSTITUTION: A positive type electrostatic liq. developer is composed of a nonpolar liq. having a kauri-butanol value of <=30 and accounting for most of the developer, thermoplastic resin particles having <=10μm area average particle size and contg. an org. S-contg. compd. practically insoluble in the nonpolar liq. or immiscible with the liq. at ambient temp. in a dispersed state as an auxiliary selected form among compds. represented by formula I-III or salts of the compds. and an ionic or amphoteric compd. soluble in the nonpolar liq. as an electric charge controlling agent. In the formulae, R is a 1-30C alkyl, 6-30C aryl, etc. Improved image quality and suppressed defacing are ensured.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to electrostatic liquid developers, and more particularly to positive liquid developers containing resin particles having certain organic sulfur-containing compounds dispersed therein. This invention relates to an electrostatic liquid developer of the type.

[Background of the invention]

It is known that electrostatic latent images can be developed with toner particles dispersed in an insulating, non-polar liquid. Such dispersed materials are known as liquid developers or liquid toners. An electrostatic latent image is created by providing a photoconductive layer with a uniform electrostatic charge and then discharging the electrostatic charge by exposure to a modulated beam of radiant energy. Other methods for creating electrostatic latent images are also known. For example, one method is to provide a carrier with a dielectric surface and transfer a pre-formed electrostatic charge to this surface. Useful liquid toners are comprised of a non-polar liquid dispersion medium and a thermoplastic resin. Suitable colorants, dyes or pigments, etc. are generally present. The colored toner particles typically have a high volume resistivity, exceeding 109 ohm cm.
It is dispersed in a non-polar liquid with a low dielectric constant of less than 3.0 and a high vapor pressure. The toner particles have an average area size of 10H or less as measured by Horipa's CAPA-500 centrifugal automatic particle analyzer. After the electrostatic latent image is formed, the image is developed with colored toner particles dispersed in the non-polar liquid carrier medium, and the image is then transferred to a carrier sheet.

A liquid composed of a thermoplastic resin, a non-polar liquid dispersion medium, and preferably a colorant, since the production of a suitable image is related to the difference in charge between the electrostatic latent image being developed and the liquid developer. It is known that it is preferable to add charge control agents and preferably auxiliary agents such as polybutylene succinimide, aromatic hydrocarbons, etc. to the developer solution.

Although such developers give images of good resolution, charging and image properties have been found to be particularly pigment dependent. Some suffer from poor image quality exhibiting low resolution, poor solid coverage (density), and/or image blurring. To overcome such problems, much research effort has been devoted to developing new types of charge control agents and/or charging aids for electrostatic liquid developers or toners.

The above-mentioned disadvantages can be overcome and the compositions include a nonpolar liquid dispersion medium, an ionic or zwitterionic charge control agent, a thermoplastic resin, and preferably a colorant, and the compounds of the present invention as described below. It has been found that an improved positive-working electrostatic liquid developer can be produced. When this improved electrostatic liquid developer is used to develop electrostatic latent images, it provides improved image quality, reduced collapse, and improved solid coverage, regardless of the pigments and charge control agents present. is obtained.

[Description of the invention]

In accordance with the present invention, an improved positive-acting electrostatic liquid developer having improved charging and imaging properties essentially consists of: a non-polar liquid, (B) an organic sulfur-containing compound that is substantially insoluble or immiscible in the non-polar liquid at ambient temperature; and (4) any one of (1), (2) and (3) above. salts(
Here, R is a C1-3° alkyl group, a 01-s0 substituted alkyl group, cm-s. aryl group, C6~. thermoplastic resin particles having an auxiliary agent selected from the group consisting of substituted aryl groups) dispersed therein, the resin particles having an average particle size by area of less than lOμ , and (C) an ionic or zwitterionic charge control agent compound soluble in a non-polar liquid.

In accordance with embodiments of the present invention, to make an electrostatic liquid developer for electrostatic imaging, (A) a non-polar liquid dispersion medium having a Cowrie-butanol value of 30 or less, a thermoplastic resin, and A sulfur-containing compound group of the following formula, and (4) salts of the above (1), (2) and (3),
at an elevated temperature, during which the temperature in the apparatus is sufficient to plasticize and liquefy the resin, and the non-polar liquid dispersion medium is denatured and the resin decomposes. (B) cool the dispersion by any of the following techniques to (1) form a gel or solid mass without stirring; (2) agitation until a viscous mixture is formed and grinding with a grinding medium, with or without additional liquid; (2) stirring until a viscous mixture is formed; or (3) continue to grind with a grinding media to prevent the formation of gels or solid clumps in the presence or absence of additional liquid; (C) particle size of 10 μm or less; a toner particle dispersion having an area average of A
), a method for producing a positive electrostatic liquid developer is provided.

Throughout the specification, the following terms have the following meanings:

In the claims, "consisting essentially" means that unspecified components that do not interfere with the characteristics of the developer are not excluded from the composition of the electrostatic liquid developer. . For example, in addition to the main components, additional components may be present, such as colorants, finely divided oxides, adjuvants such as polybutylene succinimide, aromatic hydrocarbons, alkylhydroxybenzyl polyamines, etc. Can be done.

Q/m is the charge to mass ratio expressed in microcoulombs/g.

The electrical conductivity is the electrical conductivity (pmhos/cm) of the developer measured at 5 Hz 5 V and is expressed as BULK.

Grayscale refers to a step wedge in which the image density increases at a constant rate from I)min to DnliLX.

The non-polar liquid dispersion medium (A) is preferably a branched aliphatic hydrocarbon, more preferably Isovar 0-G1 Isovar ■-H, Isovar 0- to 1 Isovar ■-L1 Isovar 0-M and Isovar ■-■
It is. These hydrocarbon liquids are narrow range fractions of isoparaffinic hydrocarbons with extremely high levels of purity. For example, the boiling point range of isovar [F]-G is 157°C to 176°C, and isovar [F]
]-H is 176℃~191'O, isobar■-
177°C to 197°C, isobar [F] - 1
88°C to 206°C and Isobar ■-M is 207°
O ~ 254℃ ~ Isopal @ -V Ha 254.4℃ ~
It is 329.4°0. Isobar 0-L is 194℃
It has an intermediate boiling point in the vicinity. Isobar■-M is 8
It has a flash point of 0°C and an ignition point of 338°C. Strict manufacturing standards limit sulfur, acids, carboxyl, chloride, etc. to a few ppm. They are virtually odorless, with only a very slight paraffin odor. They have excellent stability and are all manufactured by Exxon. High purity normal paraffin liquid, Exxon's Norval ■12. Norpar 013 and Norpar 015 can also be used. These hydrocarbon liquids have the following flash points and ignition points: Liquid Flash Point (°C) Ignition Point (°C)
) Norpearl 612 69 20
4 Norbar■13 93 21
0 norbar■15 118 2
10 This non-polar liquid dispersion medium is all IO 1 ohm CI
It has a volume electrical resistance value exceeding I+ and a dielectric constant of 3.0 or less. The vapor pressure at 25°0 is less than 10 Torr. Isovar [F]-G has a flash point of 40°C as measured by the tag closed cup method, and Isovar 0-H has a flash point of 40°C as measured by the tag closed cup method.
It has a flash point of 53°C as measured by TM D65.

Isovar [F]-ri and Isovar 0-M have flash points of 61'O and 80<0>C, respectively, measured by the same method. Although these are the preferred non-polar liquid dispersions, the key properties of all suitable non-polar liquid dispersions are:
These are the volume electrical resistance value and the dielectric constant. In addition to this, one feature of the non-polar liquid dispersion medium is a low cowry-butanol value of 30 or less, preferably around 27 or 28 as measured by ASTM D1133.

In producing liquid developers, the proportion of thermoplastic resin to non-polar liquid dispersion medium is such that the combination of components is liquefied at the operating temperature. Non-polar liquids are
It is present in an amount of 85 to 99.9% by weight, preferably 97 to 99.5% by weight, based on the total weight of the liquid developer. The total weight of solids in the liquid developer is between 0.1 and 15%, preferably between 0.5 and 15%.
It is 3.0% by weight. The total weight of solids in the liquid developer is
It is based primarily on the resin and the pigment components present, including components dispersed therein.

Useful thermoplastic resins or polymers include: ethylene vinyl acetate (EVA) copolymers (E.I. du Pont de Nemours' L-Pax resin), acrylic acid and methacrylic acid; β-
Copolymer of ethylenically unsaturated acid and ethylene, ethylene (80-99.9%)/acrylic or methacrylic acid (20-0%)/methacrylic or acrylic acid C!
, copolymers of alkyl esters (0-20%), polyethylene, polystyrene, isotactic polypropylene (crystalline), ethylene ethyl, sold by Union Carbide under the trade names Bakelite DPD 6169, DPDA 6182 Natural and DTDA 9169 Natural. Acrylate series, also sold by Union Carbide, ethylene vinyl acetate resins, such as DQDA 6479 Natural and DQDA 6832 Natural 7, EI du Pont de Nemo Earth's Sururin [F] ionomer resin, or mixtures thereof, polyesters , polyvinyltoluene, polyamide, styrene/butadiene copolymers and epoxy resins. Terpene-based polymers, such as those described in Tsuneda, US Pat. No. 4,259,428, cannot be used in the present invention because of their relatively high solubility in non-polar solvents. A preferred copolymer is a copolymer of ethylene and an α,β-ethylenically unsaturated acid, either acrylic acid or methacrylic acid. A method for synthesizing this type of copolymer is described by Rees
No. 3,264,272, which is incorporated herein by reference.

For purposes of making the preferred copolymers, the reaction of ionizable metal compounds with acid-containing copolymers as described in the Roes patent is excluded. The ethylene component is present at about 80-99.9% by weight of the copolymer and the acid component is present at about 20-0.1% by weight of the copolymer. The acid number of the copolymer ranges from 1 to 120, preferably from 54 to 90. The acid value is the number of m9 of potassium hydroxide required to neutralize 1 g of polymer. Melt index values of lO~500 Cg/10 min) are determined by ASTM D1238 Method A. Particularly preferred copolymers of this type have acid numbers of 66 and 60 and 10
They have melt index values of 0 and 500, respectively.

The aforementioned thermoplastic resin can have one of the following organic sulfur-containing compounds dispersed therein, where R is a C3-3° alkyl group, such as methyl, ethyl, propyl. , butyl, pentyl, hexyl, decyl, dodecyl, hexadecyl, pentadecyl, etc.; C1
~,. substituted alkyl and C1~. Substituted aryl, substituents include, for example, Br, CQ, halogen such as F, hydroxy, C1~. Alkoxy, C, ~. such as allyloxy; c, ~,. aryl groups such as benzene, naphthalene, anthracene, pentacene, pentathrene, etc.; and salts of (1), (2) and (3),
Examples of cations include Na, K, Ba, Ca,
These include Mg, Mn1Aff, and NH3. This sulfonic acid, organic sulfonate, organic sulfuric acid, sulfinic acid,
or these salts are substantially insoluble in non-polar liquids at ambient temperatures.

Suitable sulfur-containing compounds include: Sulfonic acids (Structure 1 above) P-)Toluenesulfonic acid p-Toluenesulfonic acid Barium 2-bromoethanesulfonate Sodium 3-Hydroxy-1-propanesulfonic acid Sodium benzenesulfonate l-butanesulfonate Sodium l-butanesulfonate ■-Sodium decanesulfonate Sodium l-dodecanesulfonate Tetradecanesulfonate Sodium tetradecanesulfonate 4-Bromo-1-butanesulfonate Sodium 4-hydroxybutanesulfonate l-pentanesulfonic acid l-Sodium pentanesulfonate 1-Sodium hexanesulfonate 1.4-Disodium butanedisulfonate 1.4-Magnesium butanedisulfonate 1.3.6.8-Pyrenetetrasulfonate tetrasodium 2- Propanesulfonate Sodium propanesulfonate Naphthalene 1.3.6-Sodium trisulfonate 8-
Sodium hydroxy-1,3,6-pyrenetrisulfonate Sodium benzenetrisulfonate Dodecylbenzenesulfonate Ethanesulfonate Cyclohexylmethanesulfonate Organic sulfuric acid (2 of the above structure) Sodium decyl sulfate Sodium lauryl sulfate Ammonium dodecyl sulfate Lithium dodecyl sulfate 3-isopropyl sulfate Sodium butyl sulfate, n-butyl sulfate, pentyl sulfate, n-undecyl sulfate, estriol, sodium trisulfate, myoinositol, potassium exasulfate, and sodium dodecyl sulfate, sulfinic acid (3 in the above structure), p-toluenesulfinic acid, benzenesulfinic acid, zinc benzenesulfinate, and sodium oxy-4,4-bis(benzenesulfinic acid) sulfur-containing compound, based on the total weight of solids in the developer.
．． It is dispersed in the solids of the developer in an amount of 1-10% by weight, preferably 1-5% by weight. The method by which the sulfur-containing compound is dispersed into the thermoplastic resin is described below.

In addition to this, the resin has the following favorable properties: 1. It is capable of dispersing auxiliaries, colorants, such as pigments, etc. 2. It is insoluble in the carrier liquid at temperatures below 40°C and
Therefore, the resin does not dissolve or solvate during storage; 3. It can be solvated at temperatures above 50°C; 4. It has a diameter of 0.1 to 5. Horiba CAPA, manufactured by Horiba Keiki Co., Ltd., between 5 μm (preferred size); −
Using a 500 centrifugal particle analyzer with a solvent viscosity of 1-24 cps, a solvent density of 0.76 g/cc, and a centrifugal rotation of 11,000 rpm, sample concentration was 1.32, and particle size range was 0.01-1.
0 μm or less, and particles of 10 μm or less (on average by area) as measured with a particle size cut of 1.0 μm, and approximately 30 μm as measured with the Malvern 3600E particle meter described below.
It can form particles with an average particle size of μm and can melt at temperatures above 6.70°C.

Above 3. The solvation causes the resin forming the toner particles to swell, gelatinize or soften.

The ionic or zwitterionic charge control agent compound (C) soluble in the non-polar liquid should be present in an amount of 0.1" 1 per gram of developer solids.
0.0001119, preferably 1 = 1.000m
positive charge control agents, such as Enphos D70-30G and Enphos F27-
Glyceride charge control agents such as Lecithin, a division of Liteco Chemical Company, are sodium salts of phosphorylated mono- and diglycerides with unsaturated and saturated acid substituents, respectively, both sold by Liteco Chemical Company. Barium petronate ■, neutral barium petronate [F], basic calcium petronate [F]
, neutral calcium betronate ■, oil-soluble petroleum sulfonate, etc.

As previously mentioned, additional components that may be present in electrostatic liquid developers are colorants such as pigments or dyes and combinations thereof, which may not be necessary in certain applications. However, they are preferred to be present to make the latent image visible. Coloring agents, such as pigments, may be added in an amount of approximately 60% by weight, based on the total weight of developer solids.
It can be present in amounts up to % by weight, but preferably amounts from 0.01 to 30% by weight.

The amount of colorant can be varied depending on the use of the developer. An example of pigment is Monastral Blue G (C
, 1, Pigment Blue 15, C, I.

No. 74160), Toluidine Red Y (C, 1,
Pigment Red 3), Kind 0 Magenta (Pigment Red 122), Kind Brilliant Scarlet (Pigment Red 123, C, 1, No. 7114)
5), Toluidine Red B (C, 1, Pigment Red 3), Latch Jung 0 Red B (C, 1, Pigment Red 48), Permanent Lupin F6B13-17
31 (Pigment Red 184), Hansa Yellow (
Pigment Yellow 98), Dalamar [F] Yellow (Pigment Yellow 74, C, 1, No, 11741), Toluidine Yellow G (C, 1, Pigment Yellow L),
Monastral 0 Blue B (C, 1, Pigment Blue 15), Monastral 0 Green B (C, i Pigment Green 7), Pigment Scarlet (C, 1, Pigment Red 60), Alaric Brown (C, l
.

Pigment Brown 6), Monastral [F] Green G (Pigment Green 7), Carbon Black, Cabot 0 Mogul L (Black Pigment, C, 1, No.
, 77266) and Sterling ■NS N774 (
Pigment Black 7, C, 1, No. 77266), etc.

Fine particle size oxides such as silica, alumina,
Titania, preferably about 0.5 μm or less, can be dispersed in the liquefied resin. These oxides may be used alone or in combination with colorants. Metal particles can also be added.

Another additional component of the electrostatic liquid developer is an adjuvant selected from the group consisting of polybutylene succinimide, aromatic hydrocarbons with a cowry-butanol value greater than 30, and alkylhydroxybenzyl polyamines.

This adjuvant is generally 1 to 1.0 per gram of developer solids.
00+g, preferably in an amount of 1 to 200119. Examples of various such adjuvants include: Polybutylene succinimide: 0LOA @ -1200 sold by Chevron, analytical data K.
ose1 U.S. Patent No. 3.9.00,412 No. 2
Found in Column 0, Lines 5-13, and listed for reference; about 600 of the Amco 575 with number average molecular weight (by vapor pressure osmosis) Amco 575 contains 40-45% surfactant, 36% aromatic hydrocarbons, and the remainder is oil, etc.; aromatic hydrocarbons: benzene, toluene, naphthalene. , substituted benzene and naphthalene compounds such as trimethylbenzene, xylene, dimethylethylbenzene, ethylmethylbenzenelopylbenzene, Aromatic II 100, which is manufactured by Exxon, C, and C1. It is a mixture of alkyl-substituted benzenes.

, where a is 2 to 8, b is 1 to 10, and R is an alkyl group having 1 to 20,000 carbon atoms, and is soluble in a nonpolar liquid. .

The benzylamine group (-PN-) is linked by a methylene group to form H-PN-CH! -PN-H, H-PN-C
H2-NP-HlH-PN-CH. -NP-CH,
forming compounds such as -PN-H and others.

Preferably, at least some R groups have 50 or more carbon atoms. The hydroxy or amine of the alkylhydroxybenzyl polyamine can be further varied. For example, poron halides such as poron trifluoride, boron triiodide, and boron trichloride can form intermediates with phenolic hydroxy groups, ie, hydroxy substituents on the benzene ring. Poron oxide, poron oxide hydrate, poron trifluoride, poron triiodide, poron tribromide, poron trichloride, boric acid, poron acids (alkyl-B-(O
H)! and allyl-B-(OH), etc.), tetraboric acid, metaboric acid, and esters of boric acid, as well as primary and secondary amino groups (-NH, and -NH), as well as phenolic hydroxyl groups, etc. Intermediates can be formed with polar groups. Suitable copolymers of this type are commercially available compounds, such as the copolymers sold by Amoco Petroleum Activity, which may differ in molecular weight. Amoco 9250 is said to have a number average molecular weight (measured by osmosis) in the range of 1600-1800 and is made by reacting phenol with polybutene to form an alkylphenol, which is reacted with an amine and then reacted with an aldehyde.

It is believed that Amoco 595 and Amoco 9250 were made in a similar manner to that used to make Amoco 9040 described above.

Amoco 595 (surfactant 45%, aromatic hydrocarbon 30%)
%, and sold as oil) and Amoco 92
50 (surfactant 40-45%, aromatic hydrocarbon 36%
% and sold as oil content) have a number average molecular weight of 1000 and 1600-1800. Number average molecular weight can be measured by a technique known as permeation.

The particles in the electrostatic liquid developer have an average particle size by area of less than 10 micrometers, preferably less than 5 micrometers by weight. Although the resin particles of the developer may or may not be formed with a plurality of fibers extending integrally therefrom, the formation of fibers extending from the toner particles is preferred. The term "fiber" as used herein refers to colored toner particles formed in the form of fibers, tendrils, trichomes, floccules, hair roots, strings, hairs, hairs, etc. It means that.

Positive base electrostatic liquid developers can be produced by various methods. For example, attritors, heated ball mills, heated vibratory mills such as the Subeco Mill from Subeco with grinding media for dispersion and grinding, Ross 2 from Charles Ross and Son
At least one of the aforementioned thermoplastic resins, an organic sulfur-containing compound, and a liquid dispersion medium in suitable mixing or compounding equipment, such as a heavy-duty mixer or a double-roll heating mill (no need for grinding media). can be entered. - For boat fishing, the resin, non-polar liquid dispersion medium and optional colorant are placed in the device before the start of the dispersion process. Optional colorants can be added after the resin and non-polar liquid dispersion medium are homogenized. Polar additives can also be included in the device, for example up to 100% based on the total weight of the liquid, including non-polar liquid dispersion medium.

The dispersion process is generally carried out at elevated temperatures. That is, the temperature of each component in the equipment is sufficient to plasticize and liquefy the resin, but the non-polar liquid dispersion medium and polar additives, if present, are denatured and the resin and/or colorants are The temperature is below the point at which it decomposes. The preferred temperature range is 80° to 120°C. However, other temperatures may be suitable depending on the particular components used. The presence of grinding media that moves erratically in the equipment
Preferred for making toner particle dispersions. however,
Other agitation means can be used as well to create toner particle dispersions of appropriate size, arrangement, and morphology.

Useful grinding media include granular materials such as stainless steel, carbon steel, alumina, ceramics, zirconium, silica,
and sillimanite, and are selected from the group consisting of spherical, cylindrical, etc.

Carbon steel grinding media are particularly useful when colorants other than black are used. Typical diameter ranges for grinding media range from 0.04 to 0.5 inches (1.0 to about 13 mm).

After dispersion of each component in the apparatus in the presence or absence of polar additives, the dispersion is typically heated in the liquefied mixture for 2 hours at temperatures ranging from 00 to 50°C until the desired dispersion is achieved. is cooled to Cooling, e.g., while grinding with grinding media to prevent the formation of gels or solid lumps.
in the same equipment, such as a mill; allow a gel or solid mass to form without stirring; then break up the gel or solid mass and grind with a grinding medium; or form a viscous mixture. This can be done by stirring until the mixture is mixed and grinding with a grinding medium, etc. Additional liquid may be added at any stage during the manufacture of electrostatic liquid toners to facilitate milling or to dilute the toner to the appropriate percent solids required for toning. can. Additional liquid means a non-polar liquid dispersion medium, a polar liquid, or a combination thereof. Cooling is accomplished in a manner known to those skilled in the art, such as by circulating cold water or coolant through an external cooling jacket adjacent to the dispersion device, or by allowing the dispersion to cool to ambient temperature. It is not limited. The resin precipitates from the dispersion during this cooling. Toner particles with an average particle size (by area) of 10 μm or less, as measured by the aforementioned Horiba Centrifugal Particle Analyzer or other comparable equipment, are formed by a relatively short time of attrition.

Another instrument for measuring average particle size is the Malvern 3600E particle size meter manufactured by Malvern Corporation.
It uses laser diffraction light scattering of a stirred sample to measure average particle size. These two instruments use different techniques to measure average particle size, so the values are different. The correlation between the average sizes of toner particles in micrometers (μm) for these two instruments is: 9.9 + 3.4 6.4 + 1.9 4.6 + 1.3 2.8 + 0.8 1.0 + 0.5 0. 2+0. The correlation was obtained by statistical analysis of mean particle size values for 67 electrostatic liquid developer samples (not of the present invention) obtained by two instruments. Expected Horiba values were determined using linear regression with 95% confidence limits. For purposes of the claims herein, particle size values are as measured using a Horiba instrument.

After cooling, and after separating the toner particle dispersion from the grinding media, if present, by means known to those skilled in the art, the toner particle concentration in the dispersion is reduced and the toner particles are electrostatically charged with a predetermined polarity. A charge can be applied or a combination of these variations can be performed. The toner particle concentration in the dispersion is reduced by the addition of additional non-polar liquid dispersion medium as described above. Dilution is usually 0.1 to 15 for non-polar liquid dispersion medium! Amount%, preferably 0.3-3.0
, and more preferably to a toner particle concentration of between 0.5 and 2% by weight. ionic or zwitterionic charge control agent compounds (C) of the type previously indicated;
One or more of these can be added to impart a positive charge. This addition can be made at any time during the process; preferably at the end of the process, for example after grinding media has been removed if used and when adjusting the toner particle concentration. If a diluent non-polar liquid dispersion medium is added, the charge control agent can be added prior to, simultaneously with, or after. It is believed that upon addition of the charge control agent compound, some leaching of the organic sulfur-containing compound into the non-polar liquid dispersion medium will occur. Unless auxiliary compounds of the aforementioned type, such as polybutylene succinimide, aromatic hydrocarbons, alkyl hydroxyl benzyl polyamines, etc., have already been added during the preparation of the developer, either before or after the charge is imparted to the developer. can be added. Preferably the adjuvant compound is added after the dispersion step.

Two other specific methods for making electrostatic liquid developers include the following steps: (A) nonpolar with a cowry-butanol value of 30 or less to form a solid mass; In the absence of liquid dispersion medium,
dispersing the thermoplastic resin, an optional colorant, and/or one of the organic sulfur-containing compounds of the present invention; (B) breaking up the solid mass; (C) breaking up the broken solid mass; grinding with a grinding media in the presence of a liquid selected from the group consisting of a polar liquid with a cowry-butanol value of at least 30, a non-polar liquid with a cowry-butanol value of 30 or less, and combinations thereof; D) separating a toner particle dispersion having an average particle size by area of 10 μm or less from the grinding media; (E) adjusting the toner particle concentration to the liquid from 0.1 to 15.0;
and (F) adding to the dispersion a non-polar liquid soluble ionic or zwitterionic charge control agent compound. and (A) in the absence of a non-polar liquid dispersion medium with a Cowrie-butanol value of 30 or less to form a solid mass;
dispersing the thermoplastic resin, an optional colorant, and/or one of the sulfur-containing compounds of the present invention; (B) breaking up the solid mass; and (C) dispersing the crushed solid mass for 30 minutes. cowrie below
Redispersion in the presence of a non-polar liquid dispersion medium with a butanol value and optionally a colorant at an elevated temperature in the apparatus, during which the temperature in the apparatus is sufficient to plasticize and liquefy the resin. (D) cooling the dispersion by one of the following methods: 1) forming a gel or solid mass without agitation, then breaking up the gel or solid mass and grinding with a grinding medium in the presence or absence of additional liquid; (2) viscosity; (3) formation of a gel or solid mass in the presence or absence of additional liquid; or (3) formation of a gel or solid mass in the presence or absence of additional liquid. (E) Separate the toner particle dispersion having an average particle size by area of 10 μm or less from the grinding media; (F) Continue to grind the toner particle concentration in the liquid by 0.1. ~15゜0
Adding additional non-polar liquid, polar liquid or a combination thereof to reduce between % by weight; and CG'') adding a non-polar liquid soluble ionic or zwitterionic charge control agent compound to this dispersion. do.

A preferred mode of the invention is described in Example 1.

Industrial Applicability The positive-acting electrostatic liquid developer of the present invention exhibits improved image quality, resolution, solid coverage (density), and detail toning, toning uniformity, and the present charge control. Reduces crushing regardless of agent or pigment.

Toner particles are mostly positively charged. The developer of the present invention is useful for copying, such as black and white office copying as well as various tones; highlight color copying or color proofing, such as copying images using standard colors of yellow, cyan, magenta and, if necessary, black. .

During copying and proofing, toner particles are applied to the electrostatic latent image and can be transferred if necessary. Other potential applications for positive-acting electrostatic liquid developers include digital color proofing, phosphorographic printing plates and resists.

In the comparative examples and examples below, percentages and parts are expressed by weight, but they are not intended to limit the invention. Melt index in each example was measured by ASTM D123g Method A; average particle size by area was measured using a Fulbell 23600 particle sizer or a Horiba CAPA5
00 centrifugal particle analyzer; weight average molecular weight was determined by gel permeation chromatography (GPC).

The image quality of the toners of the present invention was measured on a modified Servin Model 870 copier unless otherwise noted. This device is a Servin 870 copier with the modifications described below.

Mechanical modifications included the addition of a pre-transfer corona and the removal of the anodized layer from the opposing roll surface, while reducing the diameter of the roll spacer to maintain the same gap between the roll and photoconductor.

The electrical modifications were as follows: (1) The image density feedback loop from the developing electrode was cut off, and the Keisuri High Voltage Supply Device 247 manufactured by Keisuri was installed.
Electrodes are connected to the mold. (2) High voltage supply device 2 is attached to the modified opposing roll.
47 type was connected. (3) The wiring of the transfer corona was cut, and this was connected to the Torek high voltage supply device Model 610 manufactured by Torek Corporation.

This modified Servin 870 machine is used to evaluate both positive and negative tone toners, depending on the voltage and bias used. For evaluation of positive tone toners, the copier was operated in positive mode: a reversal image target was used with a true transfer corona voltage and a positive development bias. This reverse image target consists of white letters and lines on a black background.

The outline of the operation is as follows. The photoconductor is positively charged (approximately 1000 V) by the charged corona. The copy is imaged onto the photoconductor and the latter is discharged to a lower voltage (increasing order of discharge from one black area to one white area). When approached to the toning electrode, the photoconductor has an electric field on its surface such that positive toner is deposited in the white image areas and negative toner is deposited in the black image areas when present. If necessary, the toner background is cleaned by biased opposing rolls. The toner is then transferred onto the paper by a transfer corona (the transfer force is due to the negative charge applied to the back side of the paper). This toner is then heat fused. The actual voltages and biases used are indicated in each example. fl
I) / mm indicates line pair/dragon.

Table 1 contains information on toner formulations and effects.

Charge-to-mass ratio measurements in microcoulombs/g (Q/m) are shown for each toner. Toner Q
/m ratio is determined as follows: weigh the weight of a light aluminum dish, place it on the Cernoshesa,
Then, put the toner into this cell (volume between the bottom of the cell and the back side of the plate, thickness 0.060 inch - 1,52+
*fills m).

A 1809f capacitor was charged to 100 OV and placed between the cell and a Keisli 61B electrometer in series with the cell. The toner is allowed to deposit for 4 seconds. The total charge flowing through the cell is measured with an electrometer and is proportional to the charge of the deposited toner. The plate with attached toner was removed from the cell and heated at 130°C for about 2 hours.
Dry on a hot plate for 0 to 30 minutes and measure the change in weight using a Metra AE100 balance. Measured with an accuracy of Lmg. Then, the value of Q/m is Q/m-607
Calculated using the formula 6m. This process is repeated using a voltage of -1000 V to deposit developer toner particles of opposite polarity. The value of Q/m is displayed with the sign of the toner particle. The +/- ratio is the weight ratio of deposited positive toner particles to negative particles.

Table 2 shows the effects obtained with various organic sulfur-containing compounds and their solubility in non-polar liquids.

Control Example 1 The following ingredients were placed in a Union Process IS Calendar mill manufactured by Union Process Corporation: Ingredient Amount (r) Copolymer of ethylene (89%) and methacrylic acid (11%) at 190°C. Melt index 100. Acid value (iB200.00 hoikoftalb/L, -G XBT-583D.

Heubach Co., Ltd. 50.00 Isobar [F]-L; non-polar liquid with a cowriebutanol value of 27;
Milled with 5 inch (4,78+am) stainless steel balls at a rotor speed of 23 Orpm for 2 hours. While milling, it was cooled to ambient temperature, 700 g of Isovar [F].L (Exxon) was added, and milling continued.

Following milling, the average particle size was monitored. The particle size measured with a Malvern particle size meter was 8.3.
This corresponds to 16 hours of cold milling. The grinding media was removed and the toner was diluted to 2% solids with additional isovar [F]-trifluoride and charged with 40 grams of basic barium betronate (BBP) per gram of toner solids at 25 pm.
A conductivity of hos/am was obtained. Image quality was measured using a modified Servin 870 copier set up for evaluating positive toners. The copying machine has the following bias due to the reversal image target: developing section bias is +〇00V, transfer corona is -6
It was operated at kV.

The image quality was extremely poor with almost no recognizable images. The image showed areas of inverted image, indicating that the toner was negatively charged, and was an insufficient image for resolution measurements. The Q/m measurement also showed that the toner was negatively charged, with the ratio of the amount of attached positive particles/the amount of attached negative particles being 0 at Q/m--92. The results are shown in Table 1 below.

Control Example 2 The method of Control Example 1 was repeated with the following changes: no pigment was used. The toner was cold milled for 6 hours and had a final average particle size of 9.0- on a Fullbell 23800 particle sizer. The toner was diluted to 2% solids with additional Isovar ■-L and charged with 40 mg basic barium petronate [F] per gram of toner solids to give a conductivity of 29 pmhos/as. The image quality is a modified Servin 870 set for negative toner evaluation.
Measured using a copying machine. The copier was operated with standard image targets at the following biases: developer bias at +500 volts and transfer corona at +6 kV. The image quality was fair, and the toner was negatively charged. Q/m
Measurements also show that the toner is negatively charged, with Q/
m - Attached positive particle amount/adhered negative particle amount ratio at -159-
It was 〇. The results are shown in Table 1 below.

Control Example 3 The following components were placed in a Union Process O1 grinder manufactured by Union Process Co., Ltd.: Component Jl (g) Methyl acrylate (87.3%) / Methacrylic acid (3.1%) / Terpolymer of ethylhexyl acrylate (29,8%),
Weight average molecular weight 172.000, numerical value 13.35, OQ Columbia Red Medium, RD2392. 7.
0 Isovar 0-L manufactured by Baur Urich, see Control Example 1 200.0 Each component was heated to 90° to 110° C. and ground for 2 hours with a stainless steel ball 0.1875 inch (4.78 mm) in diameter. Ta. Cool to ambient temperature while milling, milling continued for 24.5 hours, and the average particle size was
-500 centrifugal automatic particle analyzer measured it to be 1.0 m. The grinding media was removed and the toner particle dispersion was diluted to 2% solids with additional Isovar [F]-trifluoride to give 266 μg of Enphos® D70-30C per gram of toner solids.
EP) to obtain a conductivity of 17 pa+hos/c+n. The image is transferred to a photoconductive film, e.g. Hotter
No. 3,314,788 and Paul
N et al., U.S. Pat.
The outer layer is an organic photoconductive layer, the inner substrate-contacting layer is an electrically conductive layer such as aluminum, and the outer layer is an organic photoconductive layer; A portion of the layer is removed along at least one edge thereof to create a strip of conductive layer, and a conductive paint such as carbon black is applied onto this exposed strip to ground the conductive layer. It is coated to make it look like this. The photoconductive film used is 0.5 inches/second (127 cm
A cathode ray tube is used to selectively discharge the charged film by passing it through a scorotron at 11,000 V at a rate of 1,000 V per second), and a developer solution is applied to the charged film using a gap filled with developer between the charged film and a 135 QV developer electrode. Toned. The image is 11
The lava was placed in a 5'F (4B"C) oven for 1 minute and cooled to ambient temperature. Using the imaging method described in this control example, an inverted or negative image is obtained.

The results are shown in Table 1 below.

Control Example 4 A toner was made as described in Example 2 with the following changes: 1-hexadecanesulfonic acid (HDSA) in place of 2-bromoethanesulfonic acid sodium salt.
．． 9 g, 200 g of Isovar ■-L and 118 g of Isovar [F]-H were added. Grinding is 27
The average particle size was 1.30 μs as measured on a Horiba CAP A-500 centrifugal automatic particle analyzer. The grinding media was removed, and the toner particle dispersion was diluted to 2% solids with Isovar [F]-trifluoride and charged with 40 mg of basic barium petronate per gram of toner solids to obtain a conductivity of 19 paths/cm. . The image quality is a modified Chibin 8 set for positive toner evaluation.
Measurements were made using a F0 copier. The copier was operated with a reversed image target at the following biases: developer bias +600V and transfer corona -6kV. The image quality is poor;
The image showed that the toner was negatively charged. The image showed a resolution of 411 p/mm with faint lines and poor density. Q/m measurement also shows that the toner is negatively charged.
Q/m --68 and a ratio of the amount of adhered positive particles to the amount of adhered negative particles -0. The results are shown in Table 1 below. A significant amount of 1-hexadecane sulfonic acid (0.04% by weight based on the amount used in the 2% solids toner) is substantially soluble in Isovar [F]-L and soluble in non-polar liquids. It is demonstrated that salts soluble in do not enhance positive charging.

The results are shown in Table 2 below.

Control Example 5 The method of Control Example 1 was repeated with the following changes: 0.80 g of p-toluenesulfonic acid (pTSA) from Fisher Scientific was added to the diluted toner carrier liquid. , no charge control agent was added and the resulting conductivity was Opihos/crn. Image quality was measured using a modified Chibin 8F0 copying machine set for evaluating positive toners. The copying machine was operated with a reversed image target at the following biases: developer bias +600v and transfer corona -6kv. The image quality was poor with a weakly faded reversed image indicating that the toner was positive or bipolar. Although the image showed a resolution of 1ONp/+n, each characteristic was not satisfactory and the density was extremely low.

The Q/m measurement shows that the toner is bipolar;
Q/m --4 and the ratio of the amount of attached positive particles to the amount of attached negative particles was -0.09. The results are shown in Table 1 below.

Control Example 6 The method of Control Example 1 was repeated with the following changes: p-toluenesulfonic acid (pT
SA) of 0.80. is added to the toner carrier liquid after dilution and charged with 4 [1a+g of basic barium betronate [F] per gram of toner solids.

An electrical conductivity of 28 pmhos/cm was obtained. Image quality was measured using a modified Chibin 8F0 copying machine set for evaluating positive toners. The copier was operated with a reversed image target at the following biases: developer bias +600V and transfer corona -6kV. The image quality was fair, with an inverted image indicating that the toner was negatively charged. This inverted image was a smeared image with faint lines with a resolution of 1 o 1 p/am and a fair density. Q
/ m measurement indicates that the toner is negatively charged, and Q
/ m''-104 and the ratio of the amount of adhered positive particles to the amount of adhered negative particles was -0. The results are shown in Table 1 below.

Example 1 The method of Control Example 1 was repeated with the following changes: 51.28 g of Heikoftal Blue G XBT-583D was used instead of 50.00. In addition, 5.13. p-toluenesulfonic acid manufactured by Fisher Scientific Co., Ltd. was added first. The toner was cold milled for 17 hours and the final average particle size on a Fullbell 23600 particle size analyzer was 4. He had Oun. The toner was diluted to 2% solids with additional isovar [F]-
It was charged with 40+wg basic barium petronate [F] per gram of toner solids to obtain a conductivity of 9 paths/cI11. Image quality was measured using a modified Servin 870 copier set up for evaluating positive toners. The copier was operated with a reversed image target at the following biases: developer bias +700v and transfer corona -6kV. The image quality was very good and the image showed that the toner was positively charged. The image showed a resolution of 7p/mm and good density. The Q/m measurement also shows that the toner is positively charged, with Q/m-+109 and the amount of attached negative particles-
It had 〇. A considerable amount of p-toluenesulfonic acid (
2% solids (0.04% by weight based on the amount used in the toner) was substantially insoluble in Isovar ■-L. The results are shown in Table 1 below.

Example 2 The following ingredients were placed in a Union Process 01 mill, manufactured by Union Process, Inc.: Ingredients
Quantity Cg) Copolymer of ethylene (89%) and methacrylic acid (11%), 35.0 at 190°C
0 Melt Index 100, Acid Value 66 Isobar ■-L, See Control Example 1 125.0 Heikoftal Blue-G
Each component manufactured by Aldrich Chemical Co., Ltd. was heated to 901-110°C, and the diameter was 0.187 mm.
With a 5 inch (4.78 mm) stainless steel ball,
Milled for 2 hours at a rotor speed of 230 rpm. The mill continues milling as it cools to ambient temperature and then
g of Isovar ■-L was added. Milling was continued for 24.5 hours and the average particle size on a Fullbell 23600 particle size analyzer was 8.2-. The grinding media was removed and the mixture was diluted to 2% solids with additional Isovar ■-L.
It was charged with 4 Qtng of basic barium betronate [F] per gram of toner solids to obtain a conductivity of 17 gmhos/an. Image quality was set for positive toner evaluation. Measurements were made using a modified Servin 870 copier. The copier was operated with a reversal image target at the following biases: developer bias +600 cm and transfer corona -6 kV. The image quality was very good and the image showed that the toner was positively charged. The images showed ION p/am resolution and good density. Q/m measurement also showed that the toner was positively charged, with Q/m-+86 and the amount of attached negative particles -0. A significant amount of 2-bromoethanesulfonic acid sodium salt (0.041 iffi% based on the amount used in the 2% solids toner) is substantially insoluble in Isovar [F]-L. The results are shown in Table 1 below.

Example 3 The method of Example 2 was repeated with the following changes = 2-
Instead of bromoethanesulfonic acid sodium salt, 3-hydroxy-1-propanesulfonic acid sodium salt (HOPSA) manufactured by Aldrich Chemical Company was used. The toner was cold milled for 23.5 hours and had a final average Malvern particle size of 7.0-. The toner was diluted to 2% solids with additional isovar [F] and charged with 40 μl of basic barium mebetronate per gram of toner solids to give a conductivity of 18 pmhos/am. The image quality is a modified Chibin 8F0 set for positive toner evaluation.
Measured using a copying machine. The copier was operated with a reversed image target at the following biases: developer bias +600 volts and transfer corona -6 kV. The image quality was very good and the image showed that the toner was positively charged. Image is 1
It exhibited a resolution of 01p/Il■ and a good density. Q
/m DI constant also showed that the toner was positively charged, with Q/m-+132 and the amount of attached negative particles -0. A significant amount of 3-hydroxy-1-propanesulfonic acid sodium salt (0.04% by weight based on the amount used in the 2% solids toner) is substantially insoluble in Isovar [F]-L. there were. The results are shown in Table 1 below.

Example 4 The method of Example 1 was repeated with the following changes: p-
) luenesulfonic acid, p-)luenesulfonic acid barium salt (Ba pTS, manufactured by Aldrich Chemical Co., Ltd.)
A) was used. The toner was cold milled for 17 hours and had a final average particle size of 3.6 particles. The toner was diluted to 2% solids with additional isovar [F] and charged with 40 mg basic barium petrolate [F] per gram of toner solids to give a conductivity of 14 pahos/cm. Image quality was measured using a modified Chibin 8F0 copying machine set for evaluating positive toners. The copying machine has the following bias due to the reversed image target: developer section bias +80
It was operated with 0V and transfer corona -6kV.

The image quality was very good and the image showed that the toner was positively charged. The image showed a resolution of 10 tlp/square and good density. Q/m measurement also shows that the toner is positively charged, with Q/m-+309 and the amount of attached positive particles/
It had an attached negative particle amount ratio of -12.5. A considerable amount of p
-Toluenesulfonic acid barium salt (0.04% by weight based on the amount used in the 2% solids toner) was substantially insoluble in Isovar [F]. The result will be in the first part later.
As shown in the table.

Example 5 The toner used was Isovar [F]-L200 instead of Niisovar ■-L125r and Isovar ■-H811g made as described in Example 2 with the following changes.
g was used and 0.9 g of benzene sulfonic acid (B2SA) from Aldrich Chemical Co. was added in place of sodium 2-bromoethanesulfonate. Each component was heated to 90°-110°C and milled for 3 hours. The mill was cooled to ambient temperature while continuing milling. Milling lasted for 27 hours and the average particle size was 1.59- as measured on a Horiba CAP A-500 centrifugal automatic particle analyzer. The grinding media was removed, and the toner particle dispersion was then diluted to 2% solids with additional isovar [F] and charged with 40g+g of basic barium vetronate per gram of toner solids to a concentration of 6 pmhos/cm. The conductivity was obtained. Image quality was measured using a modified Chibin 8F0 copier set up for positive toner evaluation. The copying machine was operated with a reversed image target and the following biases: developer section bias +000 V and transfer corona -6 kV. The image quality was very good and the image showed that the toner was positively charged. Q/m measurements also showed that the toner was positively charged, with Q/m = +51 and an amount of negative particles attached -0. An equivalent amount of benzenesulfonic acid (0.04% based on the amount used in the 2% solids toner)
'r! X amount %) was substantially insoluble in Isovar [F]-L. The results are shown in Table 1 below.

Example 6 The procedure of Example 2 was repeated with the following changes: 40 g of resin was used instead of 35 g, and 0.82 g of paratoluenesulfonic acid was used instead of 2-bromoethanesulfonic acid.
g and no pigment was used.

During the cold grinding process, additional isobar ■-L is 88g
125g was added instead. The toner was cold milled for 23 hours and had a final average particle size of 11.0 m. The toner was diluted to 2% solids with additional isobar and charged with 40a+g of basic barium petrolate [F] per gram of toner solids to 250pmhos.
A conductivity of /cm was obtained. Image quality was measured using a modified Chibin 8F0 copier set up for positive toner evaluation. The copier is biased by the reversed image target as follows:
It was operated with a developing section bias of +500 V and a transfer corona of 6 kV. The image quality was very good, with an inverted image indicating that the toner was positively charged. The image shows fine line toning and good density.

fIp/+am could not be measured because there was no pigment in the image. Q/m measurements also showed that the toner was positively charged, with a Q/rn-+573 and a negative particle amount of -0. An equivalent amount of para-toluenesulfonic acid (0.04% based on the amount used in the 2% solids toner)
% by weight) was virtually insoluble in Isovar [F]. The results are shown in Table 1 below.

Example 7 The toner was prepared with p-toluenesulfonic acid (pTS) during the thermal process.
Made as described in Control Example 3, except that 0.7 g of A) was added. Milling was continued for 22 hours, and the average particle size was on a Horiba CAPA-500 Centroid Automatic Particle Analyzer Ten"C14-. The dispersion was diluted and
charged and evaluated. The evaluation was performed as described in Control Example 3. The images showed good resolution and grayscale. The results are shown in Table 1 below.

Example 8 The method of Example 2 was repeated with the following changes = 2-
Sodium n-butyl sulfate from Lancaster Synthesis was used in place of bromoethane sulfonic acid. The toner was cold milled for 19 hours and had a final Malvern 3B00 particle size analyzer particle size of 7.8. The toner was diluted with additional isobar to 2% solids and charged with 40 g of basic barium petrolate [F] per g of toner solids to give a conductivity of 10 pmhos/am. Image quality was measured using a modified Chibin 8F0 copier set up for positive toner evaluation. The copying machine has the following bias due to the reversed image target: developer section bias +
It was operated at 1000V and transfer corona -6kV. The image quality was good and the image showed that the toner was positively charged.

The images showed 8-5 ftp/ms resolution and good density. Q/m-+30.1 and the ratio of the amount of adhered positive particles to the amount of adhered negative particles was -140. The results are shown in Table 1 below.

Table Sulfur-Containing Compounds p-Toluenesulfonic Acid (p-) Solubility in Solubility in Nonpolar Liquids ■10 kō+ kō+! + ■+ I+ A non-polar liquid with a uri-butanol value, (B) an organic sulfur-containing compound that is substantially insoluble or immiscible in a non-polar liquid at ambient temperature; Although the invention has been described in detail, the invention can be further summarized and illustrated by the following embodiments.

1) Has improved charging and imaging properties,
A positive-acting electrostatic liquid developer comprising: (A) a force less than 30 present in a predominant amount;
1), salts of (2) and (3) (where R is a C alkyl group, a C1-30 substituted alkyl group, a C aryl group "6-30 substituted aryl group)" The auxiliary agent selected from the group is thermoplastic resin particles dispersed therein, and the resin particles are 1O11
A positive-acting electrostatic liquid comprising: (C) an ionic or zwitterionic charge control agent compound soluble in a non-polar liquid; developer.

2) The sulfur-containing compound has the following formula: where R is a C alkyl group, a C8-30 substituted alkyl group, a C8-30 aryl group, a C6-30 substituted aryl group, and n is 1-4. , and salts thereof, the liquid developer described in the preceding item 1.

8) The liquid developer according to item 2 above, wherein the sulfur-containing compound is p-toluenesulfonic acid.

4) The liquid developer according to item 2 above, wherein the sulfur-containing compound is barium salt of p-toluenesulfonic acid.

5) The sulfur-containing compound has the following formula: (where R is a C alkyl group "1-30 substituted alkyl group, C aryl group" 6-30 substituted aryl group,
and n is 1 to 6), and the liquid developer according to item 1 above, which is a salt thereof.

6) The liquid developer according to item 5 above, wherein the sulfur-containing compound is n-butyl sodium sulfate.

7) The liquid developer according to item 5 above, wherein the sulfur-containing compound is sodium decyl sulfate.

8) Based on the total weight of the liquid developer, component (A) is 85~
99.9% by weight, total weight of developer solids 0.1-15.
0% by weight and component (C) is present in 1g of developer solids.
- The liquid developer according to item 1, which is present in an amount of 0.1 to 10,000 mg per liter.

9) Sulfur-containing compounds are o based on the total weight of developer solids.
, 1-io% by weight of the liquid developer according to item 8 above.

10) The liquid developer according to item 1 above, wherein up to 60% by weight of the colorant is present, based on the total weight of the developer solids.

11) The liquid developer according to item 10 above, wherein the coloring material is a pigment.

12) The liquid developer according to item 10 above, wherein the colorant is a pigment.

13) An oxide with a microparticle size is present;
The liquid developer described in 1 above.

14) Liquid developer according to paragraph 1, wherein an additional component is present, which is an adjuvant selected from the group consisting of polybutylene succinimide, aromatic hydrocarbons and alkylhydroxybenzyl polyamines.

15) Liquid developer according to paragraph 10, wherein an additional component is present, which is an adjuvant selected from the group consisting of polybutylene succinimide, aromatic hydrocarbons and alkylhydroxybenzyl polyamines.

1B) The liquid developer according to item 14 above, wherein a polybutylene succinimide auxiliary compound is present.

17) The liquid developer according to item 14 above, wherein an aromatic hydrocarbon auxiliary compound is present.

18) The liquid developer according to item 1 above, wherein the thermoplastic resin is a copolymer of ethylene and an α,β-ethylenically unsaturated acid selected from the group consisting of acrylic acid and methacrylic acid.

19) The liquid developer according to item 1 above, wherein the thermoplastic resin is polystyrene.

20) Thermoplastic resin is ethylene (80-99.9%)/
Acrylic or methacrylic acid (20-0%) / C1-5 alkyl ester of acrylic or methacrylic acid (
The liquid developer according to item 1 above, which is a copolymer of 0 to 20%).

21) Thermoplastic resin is ethylene (80-99.9%)/
Acrylic or methacrylic acid (20-0%) / C1-5 alkyl ester of acrylic or methacrylic acid (
11. The liquid developer according to item 10 above, which is a copolymer of 0 to 20%).

22) The liquid developer according to item 20 above, wherein the thermoplastic resin is a copolymer of ethylene (89%)/methacrylic acid (11%) and has a melt index value of 100 at 190°C.

23) The liquid developer according to item 1 above, wherein the particles have an average particle size of 5 or less by area.

24) The liquid developer according to item 1 above, wherein component (C) is an oil-soluble petroleum sulfonate.

25) The liquid developer according to item 1 above, wherein component (C) is lecithin.

26) A method for making a positive electrostatic liquid developer for electrostatic imaging, comprising: (A) a non-polar liquid dispersion medium having a cowry-butanol value less than 30, a thermoplastic resin; and a sulfur-containing compound of the following formula, and (4) salts of the above (1), (2) and (3) (
where R is an alkyl group of C selected from the group consisting of a substituted alkyl group of 1-30, an aryl group of C and a substituted aryl group of $-30, and dispersed at an elevated temperature, During this time, the temperature in the apparatus is maintained at a temperature sufficient to plasticize and liquefy the resin and below the temperature at which the non-polar liquid dispersion medium is denatured and the resin decomposes; Either technique may be used, namely (1) forming a gel or solid mass without stirring, then breaking up the gel or solid mass, and grinding with a grinding media in the presence or absence of additional liquid. (2) stirring until a viscous mixture is formed and grinding with a grinding medium, with or without additional liquid; and (3) in the presence or absence of additional liquid. (C) continue milling with a milling media to prevent the formation of gels or solid clumps; and (D) adding an ionic or zwitterionic charge control agent compound soluble in a non-polar liquid to the dispersion during or subsequent to step (A). Method of manufacturing liquid.

27) The sulfur-containing compound has the following formula: In Elm, R is a C alkyl group "1-30 substituted alkyl group, C aryl group" 8-30 substituted aryl group, and n is 1-4) or These salts are mentioned in the previous item 2.
Method described in B.

28) The method according to item 27, wherein the sulfur-containing compound is p-toluenesulfonic acid.

29) The method of item 27 above, wherein the sulfur-containing compound is 1)-toluenesulfonic acid barium salt.

30) The sulfur-containing compound has the following formula: (where R is an alkyl group of C 1-30 substituted alkyl group, aryl group of C 8-30 substituted aryl group,
and n is 1 to 6) and salts thereof.

31) The method according to item 30 above, wherein the sulfur-containing compound is sodium n-butyl sulfate.

32) The method according to item 30, wherein the sulfur-containing compound is sodium decyl sulfate.

33) In the device, in percent based on the total weight of the liquid,
27. The method of claim 26, wherein up to 100% by weight of the polar adjuvant having a Kauri-butanol value of at least 30 is present.

34) Grinding media can be stainless steel, carbon steel, ceramic,
The method according to item 2B above, wherein the sillimanite is selected from the group consisting of alumina, zirconium, silica and sillimanite.

35) The method according to item 26 above, wherein the thermoplastic resin is a copolymer of ethylene and an α,β-ethylenically unsaturated acid selected from the group consisting of acrylic acid and methacrylic acid.

36) Thermoplastic resin is ethylene (80-99.9%)/
Acrylic or methacrylic acid (20-0%) / Cl-5 alkyl ester of acrylic or methacrylic acid (
2B, wherein the copolymer is a copolymer of 0 to 20%).

87) The method according to item 3B, wherein the thermoplastic resin is a copolymer of ethylene (89%) and methacrylic acid (11%) and has a melt index value of 100 at 190°C.

38) At least one colorant is present during step (A) and the temperature is sufficient to plasticize and liquefy the resin and to denature the non-polar liquid dispersion medium such that the resin and colorant are The method according to item 2B above, wherein the inside of the device is maintained at a temperature at which decomposition is desired.

39) The method according to item 26 above, wherein the charge control agent compound is oil-soluble betroleum sulfonate.

40) The method according to item 26 above, wherein the charge control agent is lecithin.

41) The method of item 26 above, wherein the additional non-polar liquid dispersion medium, polar liquid, or a combination thereof is present in the range of 0.1 to 15% by weight with respect to the liquid to reduce the toner particle concentration. .

42) The method according to item 4) above, wherein the toner particle concentration is reduced by an additional non-polar liquid dispersion medium.

43) Cooling of the dispersion in the presence or absence of additional liquid to prevent the formation of gels or solid clumps;
The method according to item 2B above, which is carried out while continuously grinding with a grinding medium.

44) Cooling of the dispersion causes a gel or solid mass to form without stirring, then breaking up this gel or solid mass and grinding with a grinding media in the presence or absence of additional liquid. 2.
The method described in 6.

45) The method according to item 2B, wherein cooling of the dispersion is carried out by stirring until a viscous mixture is formed and grinding with a grinding medium in the presence or absence of additional liquid.

46) Polybutylene succinimide, aromatic hydrocarbon,
27. The method according to item 26, wherein the auxiliary compound selected from the group consisting of and alkylhydroxybenzyl polyamine is added to the liquid developer.

47) Polybutylene succinimide, aromatic hydrocarbon,
39. The method according to item 38, wherein the auxiliary compound selected from the group consisting of and alkylhydroxybenzyl polyamine is added to the liquid developer.

48) A method for making an electrostatic liquid developer, comprising (A
) a sulfur-containing compound of the formula: 1), salts of (2) and (3) (where R is an alkyl group of C, a substituted alkyl group of 1-ao, an aryl group of C, a substituted aryl group of 8-30); (B) crush this solid mass; (C) disperse this crushed solid mass into at least 30
grinding with a grinding media in the presence of a liquid selected from the group consisting of polar liquids with a cowry-butanol value of less than 30, non-polar liquids with a cowry-butanol value of less than 30, and mixtures thereof; (D) separating a toner particle dispersion from the grinding media, having a particle size averaged by area of 10 m or less;
(CP) addition of a non-polar liquid, a polar liquid, or a mixture thereof to reduce the weight of the dispersion to a range of A method for producing an electrostatic liquid developer, comprising:

49) A method for making an electrostatic liquid developer, comprising (A
) a sulfur-containing compound of the formula: , from the salts of (2) and (3) (where R is an alkyl group of C, a substituted alkyl group of 1-30, an aryl group of CB-30, a substituted aryl group of CB-30) (B) crushing the solid mass, and (C) dispersing the crushed solid mass in a non-polar liquid dispersion medium having a Cowrie-butanol value of 30 or less. In the presence of
redispersion at an elevated temperature in the apparatus, during which the temperature in the apparatus is sufficient to plasticize and liquefy the resin, and the non-polar liquid dispersion medium changes and the resin decomposes. (D) allowing the dispersion to form a gel or solid mass without stirring; and then breaking up the gel or solid mass; (2) Stir until a viscous mixture is formed and grind with a grinding medium in the presence or absence of additional liquid; (2) Stir until a viscous mixture is formed; or (3) milling with a grinding media in the presence or absence of additional liquid to prevent the formation of gels or solid clumps; and (E) cooling to reduce particle size to 10 W or less by area. separating the toner particle dispersion from the grinding media, having an average size of
(P) The toner concentration for the liquid is 0.1 to 15.0.
and (G) an ionic or zwitterionic charge control agent soluble in the liquid to this dispersion. A method for producing an electrostatic liquid developer comprising adding a compound.

50) At least one colorant is present during the redispersion step (C) and the temperature is sufficient to plasticize and liquefy the resin and to denature the non-polar liquid dispersion medium and cause the resin and colorant to 49. The method according to item 49, wherein the temperature in the apparatus is maintained at a temperature desired for decomposition.

earth and convenience 2 people outside

Claims (1)

Claims: 1) having improved charging and imaging properties;
A positive-acting electrostatic liquid developer comprising: (A) a non-polar liquid having a Cowrie-butanol value less than 30 present in a predominant amount; (B) a non-polar liquid at ambient temperature; Organic sulfur-containing compounds that are substantially insoluble or immiscible; , tables, etc. ▼ and (4) Salts of (1), (2), and (3) above (
Here, R is an alkyl group of C_1_ to_3_0, C_1_
A thermoplastic resin particle in which an adjuvant selected from the group consisting of a substituted alkyl group of C_6_ to_3_0, an aryl group of C_6_ to_3_0, and a substituted aryl group of C_6_ to_3_0 are dispersed therein; The particles have an average particle size by area of 10 μm or less, and (C) an ionic or zwitterionic charge control agent compound soluble in a non-polar liquid. Electrolyte liquid developer. 2) A liquid developer according to claim 1, wherein up to 60% by weight of colorant is present, based on the total weight of developer solids. 3) A liquid developer according to claim 1, wherein an additional component is present, which is an adjuvant selected from the group consisting of polybutylene succinimide, aromatic hydrocarbons and alkyl hydroxybenzyl polyamines. 4) A method for making a positive electrostatic liquid developer for electrostatic imaging, comprising: (A) a non-polar liquid dispersion medium having a Cowry-butanol value of less than 30, a thermoplastic resin; and sulfur-containing compounds with the following formulas (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (3) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and (4 ) Salts of (1), (2) and (3) above (
Here, R is an alkyl group of C_1_ to_3_0, C_1_
C_6_ to_3_0 substituted alkyl groups, C_6_ to_3_0 aryl groups, C_6_ to_3_0 substituted aryl groups) are dispersed at elevated temperature, during which time the temperature in the apparatus is such that the resin is maintained at a temperature sufficient to plasticize and liquefy and below the temperature at which the non-polar liquid dispersion medium degenerates and the resin decomposes;
(B) The dispersion is prepared by either (1) forming a gel or solid mass without stirring, then breaking up the gel or solid mass, and in the presence of additional liquid or (2) stir until a viscous mixture is formed and mill with a grinding media in the presence or absence of additional liquid; or (3) add (C) having a particle size averaged by area of 10 μm or less; The toner particle dispersion is separated from the grinding media and (D) an ionic or zwitterionic charge control agent compound soluble in a non-polar liquid is added to the dispersion during the process or in step (A).
).) A method for producing an electrostatic liquid developer comprising: 5) at least one colorant is present during step (A) and the temperature is sufficient to plasticize and liquefy the resin and to denature the non-polar liquid dispersion medium and decompose the resin and colorant; 5. The method according to claim 4, wherein the temperature in the apparatus is maintained at or below the point. 6) The method of claim 4, wherein an adjuvant compound selected from the group consisting of polybutylene succinimide, aromatic hydrocarbons, and alkylhydroxybenzyl polyamines is added to the liquid developer. 7) A method for making an electrostatic liquid developer comprising: (A) in the absence of a non-polar liquid dispersion medium having a Cowrie-butanol value of 30 or less to form a solid mass;
A sulfur-containing compound with the following formula in a thermoplastic resin: (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. Yes ▼ And (4) Salts (1), (2) and (3) above (
Here, R is an alkyl group of C_1_ to_3_0, C_1_
(B) Crushing the solid lumps, (C) This crushed solid mass is placed in the presence of a liquid selected from the group consisting of polar liquids with a cowry-butanol value of at least 30, non-polar liquids with a cowry-butanol value of less than 30, and mixtures thereof. (D) separating from the grinding medium a toner particle dispersion having a particle size averaged by area of 10 μm or less; and (E) providing a toner particle concentration of 0.1 to 15 μm with respect to the liquid. and (F) adding a liquid-soluble ionic or zwitterionic charge control agent compound to the dispersion to reduce the weight percent to a range of A method for producing an electrostatic liquid developer, comprising: adding. 8) A method for making an electrostatic liquid developer comprising: (A) applying heat in the absence of a non-polar liquid dispersion medium having a Cowrie-butanol value less than 30 to form a solid mass; A sulfur-containing compound with the following formula is contained in a plastic resin. ▼ and (4) the salts of (1), (2) and (3) above (
Here, R is an alkyl group of C_1_ to_3_0, C_1_
(B) Crushing the solid lumps, (C) This crushed solid mass is placed in the presence of a non-polar liquid dispersion medium having a Cowrie-butanol value of less than 30.
redispersion at an elevated temperature in the apparatus, during which the temperature in the apparatus is sufficient to plasticize and liquefy the resin, and below the temperature at which the non-polar liquid dispersion medium denatures and the resin decomposes. (D) the dispersion by either of the following techniques: (1) forming a gel or solid mass without stirring, then breaking up the gel or solid mass, and adding (2) stirring until a viscous mixture is formed and milling with a grinding medium in the presence or absence of additional liquid; or (3) milling with a grinding media in the presence or absence of additional liquid to prevent the formation of gels or solid clumps; (F) additional non-polar liquid, polar liquid or and (G) adding a liquid-soluble ionic or amphoteric charge control agent compound to the dispersion.